CN103215621B - A kind of compound chromium plating additive - Google Patents
A kind of compound chromium plating additive Download PDFInfo
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- CN103215621B CN103215621B CN201310046888.8A CN201310046888A CN103215621B CN 103215621 B CN103215621 B CN 103215621B CN 201310046888 A CN201310046888 A CN 201310046888A CN 103215621 B CN103215621 B CN 103215621B
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Abstract
The invention discloses a kind of compound chromium plating additive, including Organic substance and inorganic matter, described Organic substance adopts: alkane chain sulfonic acid and/or alkane chain disulfonic acid, consumption is 1-20g/L standard chromium plating liquid；Or organic compounds containing nitrogen 0.01-0.1g/L；Inorganic matter adopts: light-duty rare earth fluoride, light-duty rare earth fluoride consumption is 0.001-0.01g/L standard chromium plating liquid, and/or one of VA race element oxide, hydroxide, sulfate, the consumption of VA race element oxide or hydroxide or sulfate is 0.01-0.1g/L standard chromium plating liquid.Being added in standard Cr-plating Bath by described Organic substance and inorganic matter, not only current efficiency is high, and coating brightness is good, technique bright range width, covering power is good, and coating hardness is high, and current efficiency is high, and anode is corrosion-free, technique bright range width, covering power is good, and operating procedure is simple, and cost is low.
Description
Technical field
The present invention relates to chromium plating technical field, in particular a kind of compound chromium plating additive.
Background technology
In chrome-plated process, the first catalyst is fluorion or hexafluosilicic acid etc., and current efficiency is high, the careful light of coating, but antianode and coating matrix have corrosion, and in such solution, impurities accumulation speed is fast, and technique is difficult to control to, and coating bath is easily aging to be scrapped.Change with chain alkyl sulfonic acid or its salt, be applicable on chrome-plated process by the Politecnico in Milan the earliest, coating light, crystallization is careful, but corrosion anode and bright range are narrow, and depth capability is not good enough, Hull cell test piece 9cm, especially uses paraffin sulfonate, and coating antiseptic power declines.Rare earth addition disclosed in Chinese patent CN89105414.6, CN87102034, is all low-temperature and low-concentration chrome-plated process, but is applied in standard electric plating solution, is difficult to control technological parameter.
With halogens such as iodine for additive, current efficiency improves, because coating matrix is had activation by iodine releasing agent, but high Current Zone binding force of cladding material is poor, outward appearance dull gray, and in half light, bright range is narrow.Comprehensively utilize as additive with carboxylic acid and iodine, there is again coating crisp, the problem easily burst apart.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, it is provided that a kind of compound chromium plating additive.
In order to realize the object of the invention, the present invention provides a kind of compound chromium plating additive, and including Organic substance and inorganic matter, described Organic substance adopts: alkane chain sulfonic acid and/or alkane chain disulfonic acid, consumption is 1-20 part；With
Organic compounds containing nitrogen, consumption is 0.01-0.1 part；
Described inorganic matter adopts: light-duty rare earth fluoride, and consumption is 0.001-0.01 part, and
One of in VA race element oxide, hydroxide or sulfate, consumption is 0.01-0.1 part.
Wherein, described part is weight portion, than weight metering unit as well known to the skilled person: gram, kilogram, two etc..
Described alkane chain sulfonic acid and/or alkane chain disulfonic acid are one or more in pyrovinic acid, ammonia alkyl sulfonic acid, dimethyl sulfonic acid.Its consumption is 1-20 part, it is preferred to 2-6 part.If less than 2 parts, DeGrain；More than 6 parts, coating nucleus crystal growth is too fast, and crystal accumulation is too fast makes coating coarse.
The effect of described alkane chain sulfonic acid and/or alkane chain disulfonic acid: improve cathodic polarization and improve current efficiency, makes chromium metal simple-substance nucleus be deposited on cathode surface speed and accelerates, and such electroplating efficiency raises, the careful densification of crystallization, coating brightness is high, and corrosion resistance is strong, steady quality.
The present invention does not use sodium salt and the potassium salt of organic alkane chain sulfonic acid or alkane chain disulfonic acid or Loprazolam or ammonia alkyl sulfonic acid or dimethyl sulfonic acid or sulfamic acid or pyridine-sulfonic acid or formic acid, although the acids of above material and salt can improve cathodic polarization reaction in electroplating process, but sodium ion or potassium ion run up to a certain degree in electroplating solution, the consistency of coating will be directly affected, thus affecting the performance such as corrosion resistance that electroplating parts uses.
Described organic compounds containing nitrogen is aminoacid .gamma.-pyridinecarboxylic acid, benzotriazole, triazole, one or more in glycine, pyridine.Its preferable amount is 0.05-0.08 part.Content is low, then inconspicuous with the synergism of alkane chain sulfonic acid and/or alkane chain disulfonic acid, it is suppressed that anodic attack poor effect；Content is high, Deposit appearance dull gray.
Described organic compounds containing nitrogen is to a certain degree also improving the current efficiency of negative electrode, and reduces the interfacial tension of electroplating solution；In addition, also coordinate with alkane chain sulfonic acid and/or alkane chain disulfonic acid, the erosion of antianode in more effective suppression solution strong acid Strong oxdiative system.
Described light-duty rare earth fluoride is the fluoride of lanthanum, cerium or neodymium, it is preferred to lanthanum fluoride, cerium fluoride, neodymium fluoride etc..Its consumption is preferably 0.001-0.005 part, if content controls get Tai Gao, coating fragility can be big.
The present invention uses the fluorion of certain content, improves cathodic polarization on the one hand, also improves the plating solution activation capacity to surface of the work on the other hand, so improves the adhesion needing plating base on coating and negative electrode.And use light-duty rare earth, and on chrome-plated process, the leveling ability characteristic that rare earth has.Plating electrolytic process middle rare earth can form a cationic layer on negative electrode, when Cr VI is to movable cathode and when arriving cathode surface, it is necessary to overcome the active force of the positive field of points of rare earth ion and the mechanical resistance of rare earth ion layer.The local resistance that electric current density is more big is more big, the local resistance that electric current density is more little is more little, so need under the workpiece substrate surface configuration complex situations of plating, the region coating deposition rate that electric current density is big slows down relatively, the region coating deposition rate that electric current density is little is accelerated relatively, so the present invention makes full use of the rare earth metal Surface flat as chromium plating.
Described VA race element is arsenic, antimony or bismuth, and described VA race element oxide, hydroxide or sulfate are preferably arsenic oxide arsenoxide, bismuth oxide, stibium oxide or arsenic sulfate etc..Its preferable amount is 0.01-0.05 part, and content is little, causes suppressing anodic attack poor effect.Preferably employ itself and the mutual compatibility of organic compounds containing nitrogen, the erosion of antianode in suppression solution strong acid Strong oxdiative system effectively.
The preparation method of compound chromium plating additive of the present invention is simple, is mixed by proportioning by each composition.
Compound chromium plating additive of the present invention joins in chromium plating plating solution, and concentration generally can be controlled in 1-20g/ chromium plating plating solution, it is preferred to 1-6 gram per liter chromium plating plating solution.
The compound chromium plating additive of the present invention consumption in standard Cr-plating Bath is, for Organic substance: alkane chain sulfonic acid and/or alkane chain disulfonic acid consumption are 1-20 gram per liter standard chromium plating plating solution, it is preferred to 2-6 gram per liter standard chromium plating plating solution；It it is 0.01-0.1 gram per liter standard chromium plating plating solution with organic compounds containing nitrogen consumption, it is preferred to 0.05-0.08 gram per liter standard chromium plating plating solution；For inorganic matter: light-duty rare earth fluoride consumption is 0.001-0.01 gram per liter standard chromium plating plating solution, it is preferably 0.001-0.005 gram per liter standard chromium plating plating solution, it it is 0.01-0.1 gram per liter standard chromium plating plating solution with the consumption of VA race element oxide or hydroxide or sulfate, it is preferred to 0.01-0.05 gram per liter standard chromium plating plating solution.
Described standard chromium plating plating solution contains the sulphuric acid of 150-400 g/l of chromic anhydride and 1.5-4 g/l, operating temperature 30-75 DEG C, electric current density 15-100A/dm2。
Preferably, described standard chromium plating plating solution contains the sulphuric acid of 250 g/l of chromic anhydrides and 2.3-2.7 g/l, operating temperature 50-70 DEG C, electric current density 15-100A/dm2。
Preferably, described standard chromium plating plating solution contains the sulphuric acid of 300 g/l of chromic anhydrides and 3 g/l, operating temperature 40-60 DEG C.
Compound chromium plating additive of the present invention, alkane chain sulfonic acid and alkane chain disulfonic acid one or both, improve current efficiency, coating depositing crystalline is careful, and brightness is good.Inorganic light-duty rare earth fluoride, improves current efficiency, and coating depositing crystalline is careful, and low current district is had activation, and matrix surface oxide layer is had activation, thus improving covering power and depth capability.Using VA race element oxide, it is suppressed that anodic attack, improve electrode polarization electric current, composite first two, workpiece and anode surface do not result in corrosion and passivation.
Being added in standard Cr-plating Bath by compound chromium plating additive of the present invention, not only current efficiency is high, and coating brightness is good, technique bright range width, covering power is good, and coating hardness is high, and current efficiency is high, and anode is corrosion-free, technique bright range width, covering power is good, and operating procedure is simple, and cost is low.
Accompanying drawing explanation
Fig. 1 is 90 ° of angle experiment effect sketches of the chromium plating plating solution without compound chromium plating additive described in the embodiment of the present invention 1；
Fig. 2 is 90 ° of angle experiment effect sketches of the chromium plating plating solution containing compound chromium plating additive described in the embodiment of the present invention 1；
Fig. 3 is 30 ° of angle experiment effect sketches of the chromium plating plating solution without compound chromium plating additive described in the embodiment of the present invention 1；
Fig. 4 is 30 ° of angle experiment effect sketches of the chromium plating plating solution containing compound chromium plating additive described in the embodiment of the present invention 1.
Detailed description of the invention
Further describe the present invention by embodiment below, be conducive to the understanding to the present invention and advantage, better effects if, but described embodiment is merely to illustrate the present invention rather than the restriction present invention.
The performance parameter characterizing compound chromium plating additive of the present invention is as follows:
1. brightness: compound chromium plating additive can improve coating surface fineness, more careful and growth the speed of coating crystallization is more fast, and brightness is more good.
Use ocular estimate:
One-level (bright in mirror surface) can clearly see face and eyebrow.
Two grades (light) can clearly see face, but eyebrow sends out paste.
Three grades (half lights) somewhat have brightness, can only see face profile.
Level Four (without light) is substantially matt, only sees face profile.
2. hardness: compound chromium plating additive can strengthen coating hardness, coating hardness determines abrasion resistance when using.
Microhardness testers are used to record Vickers hardness.
3. deposit thickness: compound chromium plating additive can improve current efficiency, coating deposition rate is fast, saves production cost.
Adopt the electrolysis calibrator of anodic solution coulometry.
4. covering power: compound chromium plating additive can improve plating solution covering power and dispersibility.
Adopting test piece angle experiments: Hull cell test piece 100mm × 50mmm, centre bends in 90 ° and 30 ° of angles experiments,
5. anode loss: anode loss determines compound chromium plating additive quality good job, anode loss degree direct influence production cost.
Adopt weighing anode plating front and weight after plating, calculating difference.
Embodiment 1
Compound chromium plating additive is prepared by following weight:
Above-mentioned each composition is mixed, obtains the present embodiment compound chromium plating additive.
Containing the sulphuric acid of 150 g/l of chromic anhydrides and 1.5 g/l in chromium plating plating solution, above-mentioned compound chromium plating additive addition is 3 g/l of chromium plating plating solutions, and work processing range: temperature 30 DEG C, electric current density 15A/dm2, S anode: S negative electrode 2: 1 (cathode and anode area ratio), 1 hour time.
Through test, result is visible: whole test piece coating light is careful, and fineness presents specular light brightness, and coating hardness is high, Vickers hardness 900HV.In angle experiments, the test piece at 90 ° and 30 ° angles all has coating, as shown in Figure 2,4, and thickness 31 μm.Current efficiency 25%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.44 grams, anode loss in weight: 0.12 gram.
And only with above-mentioned chromium plating plating solution, (containing the sulphuric acid of 150 g/l of chromic anhydrides and 1.5 g/l in chromium plating plating solution, work processing range: temperature 30 DEG C, electric current density 15A/dm2, SAnode:SNegative electrode2: 1, electroplating time is traditional plating solution of 1 hour), fineness is poor, presents half light, hardness 650HV, and in right angle test, 90 ° do not have coating from middle linea angulata 15mm, and 30 ° of angles test piece linea angulata place 20mm does not have coating, as shown in Figure 1,3；Thickness 6 μm, current efficiency 12%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.22 grams, anode loss in weight: 0.34 gram.
Embodiment 2
Compound chromium plating additive is prepared by following weight:
Above-mentioned each composition is mixed, obtains the present embodiment compound chromium plating additive.
Chromium plating plating solution, contains the sulphuric acid of 300 g/l of chromic anhydrides and 3.2 g/l, 4.18 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive in Cr-plating Bath, work processing range: temperature 68 DEG C, electric current density 50A/dm2, electroplating time 1 hour.
Through test, result is visible: whole test piece coating light is careful, and fineness presents specular light brightness, and coating hardness is high, Vickers hardness 1110HV.In angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 55 μm.Current efficiency 30%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.39 grams, anode loss in weight: 0.17 gram.
And only with above-mentioned chromium plating plating solution, fineness is poor, presenting half light, hardness 790HV, in right angle test, 90 ° of centres have 5mm not have coating, and in the middle of the test piece at 30 ° of angles, intersection has 10mm not have coating；Thickness 27 μm, current efficiency 15%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.17 grams, anode loss in weight: 0.39 gram.
Comparative example 1
Adopt the plating chromium plating of common traditional standard liquid, standard Cr-plating Bath: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, not doping, electric current density 30A/dm2, temperature 55 DEG C, time 1h.
Detecting after plating, fineness is poor, presents half light, hardness 710HV, and right angle experiment has unilateral 1cm not go up coating, thickness 15 μm, current efficiency 14%, before anode weight is plated: 34.56 grams, after anode weight is plated: 34.32 grams, and anode loss in weight: 0.24 gram.
Conclusion: coating brightness is general, and anode loss is little, and current efficiency is low.
Comparative example 2 organics additive
Organics additive component is:
Pyrovinic acid: 3.3 grams
Sodium methanedisulfonate: 2.5 grams.
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.8 g/l of chromium plating plating solutions of additive, electric current density 30A/dm2, temperature 55 DEG C, time 1h.
Detect after plating, fineness presents bright in mirror surface, hardness 950HV, in angle experiments, all there is coating at 90 ° of angles, and the test piece digression line 5mm place at 30 ° of angles does not have coating, thickness 27 μm, current efficiency 28%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 30.16 grams, anode loss in weight: 4.4 grams.
Conclusion: coating brightness is good, and anode loss is serious.
Embodiment 3
Compound chromium plating additive is prepared by following weight:
Pyrovinic acid: 5.8 grams
Lanthanum fluoride 0.006 gram
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.5 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 58 DEG C, time 1h.
Detecting after plating, fineness presents bright in mirror surface, hardness 1280HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 33 μm, current efficiency 31%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 29.85 grams, anode loss in weight: 4.71 grams.
Embodiment 4
Compound chromium plating additive is prepared by following weight:
Sodium methanedisulfonate: 6 grams
Bismuth oxide 0.05 gram
Lanthanum fluoride 0.006 gram
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.2 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 58 DEG C, time 1h.
Detecting after plating, fineness presents bright in mirror surface, hardness 960HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 31 μm, current efficiency 30%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 31.31 grams, anode loss in weight: 3.25 grams.
Embodiment 5
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.3 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 58 DEG C, time 1h.
Detecting after plating, fineness presents bright in mirror surface, hardness 950HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 30 μm, current efficiency 30%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 31.46 grams, anode loss in weight: 3.1 grams.
Comparative example 3
Compound chromium plating additive is prepared by following weight:
Sodium methanedisulfonate: 5.8 grams
Pyridine-sulfonic acid 0.03 gram
Bismuth oxide 1.1 grams
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.5 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 55 DEG C, time 1h.
Detect after plating, fineness is poor, presents half light, hardness 800HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 25 μm, current efficiency 23%, high current density region has slightly burns, burn for Lycoperdon polymorphum Vitt coating, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.41 grams, anode loss in weight: 0.15 gram.
Conclusion: anode loss is light, and coating is bad.
Comparative example 4
Compound chromium plating additive is prepared by following weight:
Pyrovinic acid: 5.8 grams
0.1 gram .gamma.-pyridinecarboxylic acid
Bismuth oxide 0.02 gram
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.5 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 55 DEG C, time 1h.
Detect after plating, fineness is poor, presents half light, hardness 840HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 23 μm, current efficiency 22%, high current density region has slightly burns, burn for Lycoperdon polymorphum Vitt coating, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.46 grams, anode loss in weight: 0.1 gram.
Conclusion: anode loss is light, and coating is bad.
Embodiment 6
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.5 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detecting after plating, whole test piece fineness presents specular light brightness, hardness 1020HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 33 μm, current efficiency 32%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.48 grams, anode loss in weight: 0.08 gram.
Conclusion: anode loss is light, and coating is good, speed is fast, and hardness is high.
Embodiment 7
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.2 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detecting after plating, whole test piece fineness presents specular light brightness, hardness 1280HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 32 μm, current efficiency 31%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.5 grams, anode loss in weight: 0.06 gram.
Conclusion: anode loss is light, and coating is good, speed is fast, and hardness is high.
Embodiment 8
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.8 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detecting after plating, whole test piece fineness presents specular light brightness, hardness 890HV, in angle experiments, the test piece at 90 ° and 30 ° angles all has coating, thickness 29 μm, current efficiency 29%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.5 grams, anode loss in weight: 0.06 gram.
Embodiment 9
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5 g/l of Cr-plating Baths of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detect after plating, test piece fineness presents specular light brightness, but the current density range of specular light brightness narrows, hardness 800HV, in angle experiments, 90 ° have bright coating entirely, and the test piece interior angle 5mm place at 30 ° of angles is white coating, thickness 19 μm, current efficiency 18%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.51 grams, anode loss in weight: 0.04 gram.
Embodiment 10
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.2 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detecting after plating, test piece fineness presents specular light brightness, and high current density region exists plethora, plethora adhesion is poor, hardness 1120HV, in angle experiments, all there are bright coating, test piece limit place, namely high electric current place in 90 ° and 30 ° of angles, there is a small amount of burr, thickness 33 μm, current efficiency 34%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.51 grams, anode loss in weight: 0.05 gram.
Embodiment 11
Compound chromium plating additive is prepared by following weight:
Chromium plating plating solution: chromic anhydride (CrO3) 250g/L, sulphuric acid (H2SO4) 2.6g/L, 5.3 g/l of chromium plating plating solutions of above-mentioned compound chromium plating additive, electric current density 30A/dm2, temperature 60 C, time 1h.
Detecting after plating, test piece fineness presents specular light brightness, and high current density region exists plethora, plethora adhesion is poor, hardness 1120HV, in angle experiments, all there are bright coating, test piece limit place, namely high electric current place in 90 ° and 30 ° of angles, there is a small amount of burr, thickness 35 μm, current efficiency 36%, before the plating of anode weight: 34.56 grams, after the plating of anode weight: 34.54 grams, anode loss in weight: 0.02 gram.
The above; it is only presently preferred embodiments of the present invention; not to any formal and substantial restriction of the present invention; should be understood that; for those skilled in the art; under the premise without departing from the inventive method, also can making some improvement and supplement, these improve and supplement and also should be regarded as protection scope of the present invention.All those skilled in the art, without departing from the spirit and scope of the present invention, the equivalent variations of a little change, modification and the differentiation made when available disclosed above technology contents, it is the Equivalent embodiments of the present invention；Meanwhile, all change of any equivalent variations, modification and differentiation above-described embodiment made according to the substantial technological of the present invention, all still fall within the scope of technical scheme.
Claims (13)
1. a compound chromium plating additive, it is characterised in that include Organic substance and inorganic matter,
Described Organic substance adopts: alkane chain sulfonic acid and/or alkane chain disulfonic acid, consumption is 1-20 part and organic compounds containing nitrogen, and consumption is the combination of 0.01-0.1 part；
Described inorganic matter adopts: light-duty rare earth fluoride, and consumption is 0.001-0.01 part, and
One of in VA race element oxide, hydroxide or sulfate, consumption is 0.01-0.1 part.
2. compound chromium plating additive according to claim 1, it is characterised in that described alkane chain sulfonic acid is one or more in pyrovinic acid, ammonia alkyl sulfonic acid, dimethyl sulfonic acid.
3. compound chromium plating additive according to claim 1, it is characterised in that the consumption of described alkane chain sulfonic acid and/or alkane chain disulfonic acid is 2-6 part.
4. compound chromium plating additive according to claim 1, it is characterised in that described organic compounds containing nitrogen is aminoacid .gamma.-pyridinecarboxylic acid, benzotriazole, triazole, one or more in glycine, pyridine.
5. compound chromium plating additive according to claim 1, it is characterised in that described organic compounds containing nitrogen consumption is 0.05-0.08 part.
6. compound chromium plating additive according to claim 3, it is characterised in that described organic compounds containing nitrogen consumption is 0.05-0.08 part.
7. compound chromium plating additive according to claim 1, it is characterised in that described light-duty rare earth fluoride is the fluoride of lanthanum, cerium, praseodymium or neodymium.
8. compound chromium plating additive according to claim 7, it is characterised in that the fluoride of described lanthanum, cerium or neodymium is lanthanum fluoride, cerium fluoride, neodymium fluoride.
9. compound chromium plating additive according to claim 1 or 8, it is characterised in that described light-duty rare earth fluoride consumption is 0.001-0.005 part.
10. compound chromium plating additive according to claim 1, it is characterised in that described VA race element is arsenic, antimony or bismuth.
11. compound chromium plating additive according to claim 1, it is characterised in that described VA race element oxide, hydroxide or sulfate are arsenic oxide arsenoxide, bismuth oxide, stibium oxide or arsenic sulfate.
12. compound chromium plating additive according to claim 1 or 11, it is characterised in that described VA race element oxide, hydroxide or sulfate consumption are 0.01-0.05 part.
13. a compound chromium plating additive, it is characterised in that include Organic substance and inorganic matter, described Organic substance adopts:
Alkane chain sulfonic acid and/or alkane chain disulfonic acid, consumption is 1-20 gram per liter standard chromium plating plating solution, and organic compounds containing nitrogen, and organic compounds containing nitrogen consumption is 0.01-0.1 gram per liter standard chromium plating plating solution；
Inorganic matter adopts: light-duty rare earth fluoride, light-duty rare earth fluoride consumption is 0.001-0.01 gram per liter standard chromium plating plating solution, with one of VA race element oxide, hydroxide, sulfate, the consumption of VA race element oxide or hydroxide or sulfate is 0.01-0.1 gram per liter standard chromium plating plating solution.
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| CN102965696B (en) * | 2012-11-28 | 2015-05-20 | 郑州市大有制版有限公司 | Efficient gravure chromeplating additive |
| CN109537002B (en) * | 2018-12-07 | 2020-10-27 | 重庆立道新材料科技有限公司 | Ultrahigh-hardness chromium plating additive and application thereof |
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| US4786378A (en) * | 1987-09-01 | 1988-11-22 | M&T Chemicals Inc. | Chromium electroplating baths having reduced weight loss of lead and lead alloy anodes |
| CN101967661A (en) * | 2010-10-26 | 2011-02-09 | 广东多正化工科技有限公司 | Trivalent chromium plating solution |
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2012
- 2012-02-06 CN CN2012100247128A patent/CN102560566A/en active Pending
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2013
- 2013-02-06 CN CN201310046888.8A patent/CN103215621B/en active Active
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| CN102560566A (en) | 2012-07-11 |
| CN103215621A (en) | 2013-07-24 |
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